EP2479180A1 - Verfahren zur Herstellung von Alkylphosphaten - Google Patents

Verfahren zur Herstellung von Alkylphosphaten Download PDF

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Publication number
EP2479180A1
EP2479180A1 EP11151170A EP11151170A EP2479180A1 EP 2479180 A1 EP2479180 A1 EP 2479180A1 EP 11151170 A EP11151170 A EP 11151170A EP 11151170 A EP11151170 A EP 11151170A EP 2479180 A1 EP2479180 A1 EP 2479180A1
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EP
European Patent Office
Prior art keywords
chr
grouping
radical
water
reaction mixture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP11151170A
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German (de)
English (en)
French (fr)
Inventor
Jan-Gerd Dr. Hansel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lanxess Deutschland GmbH
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Lanxess Deutschland GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lanxess Deutschland GmbH filed Critical Lanxess Deutschland GmbH
Priority to EP11151170A priority Critical patent/EP2479180A1/de
Priority to EP12150718.0A priority patent/EP2476686B1/de
Priority to PL12150718T priority patent/PL2476686T3/pl
Priority to CA2764166A priority patent/CA2764166A1/en
Priority to US13/349,858 priority patent/US20120184764A1/en
Priority to MX2012000759A priority patent/MX345082B/es
Priority to CN201210012349.8A priority patent/CN102603792B/zh
Priority to JP2012005987A priority patent/JP6033548B2/ja
Priority to KR1020120005161A priority patent/KR101882518B1/ko
Priority to BR102012001156-5A priority patent/BR102012001156B1/pt
Publication of EP2479180A1 publication Critical patent/EP2479180A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/14—Esters of phosphoric acids containing P(=O)-halide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B63/00—Purification; Separation; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl

Definitions

  • the present invention relates to a process for the preparation of tetraalkyl bisphosphates by reacting tetrachlorobisphosphates with alcohols, neutralization of the hydrogen chloride formed with a base and separation of the salt formed in the neutralization of the reaction mixture as a concentrated aqueous solution.
  • Tetraalkyl bisphosphates are viscous, low-volatile liquids and have long been finding technical applications, for example as polymer additives (see US 2,782,128 ) or as hydraulic oils (see US 4,056,480 ). For these applications, it is typically required that the tetraalkyl bisphosphates contain as little impurities as possible. Thus, the content of acid impurities, as it can be determined for example by determining the acid number, should be as low as possible, since acid can lead to accelerated decomposition or corrosion. Tetraalkyl bisphosphates having an acid number greater than about 1.0 mg KOH / g are unusable for the applications mentioned. Like acids, base contaminants are also undesirable because they can undesirably act as catalysts in use.
  • the content of electrolytes is undesirable because it may also cause corrosion problems or may lead to incompatibility between tetraalkyl bisphosphate and a polymer matrix.
  • US 2,782,128 describes a process for preparing tetraalkyl bisphosphates by reacting dialkyl chlorophosphates with diols in the presence of pyridine.
  • the intermediate dialkyl chlorophosphate prepared in the first stage of the synthesis sequence from phosphorus trichloride, alcohol and chlorine must be worked up with the solvent benzene and then distilled in vacuo.
  • the byproduct pyridine hydrochloride must be precipitated by adding the solvent diethyl ether.
  • residues of pyridine must be extracted by means of hydrochloric acid and the product phase then acid-free with sodium hydroxide solution and with Water to be washed neutral.
  • the distillative removal of the solvent and water residues is required.
  • the total yield over both stages is given as 74-77%.
  • a disadvantage of this process is the large number of work-up operations required, the multiple use of solvents and the only moderate yield.
  • a disadvantage of this procedure is the difficulty of completely removing the pyridine residues from the final product.
  • the separation of the pyridine hydrochloride from the tetraalkyl bisphosphate by filtration succeeds only satisfactory if this dissolves only slightly in the tetraalkyl bisphosphate.
  • Another disadvantage arises from the fact that a washing of the product phase is carried out with water. If the tetraalkyl bisphosphate is partially miscible with water, losses in yield are unavoidable in this operation. For tetraalkyl bisphosphates which are miscible with water in any ratio, this laundry fails completely because a separation of the product from the wastewater by phase separation is not possible.
  • US 4,056,480 proposes a similar process for the preparation of tetraalkyl bisphosphates in which also a diol is reacted in the first stage with phosphorus oxychloride to a tetrachlorobisphosphate, which reacts in the second stage with the alcohol to the final product.
  • a dilute sodium hydroxide solution is used instead of pyridine. It forms a mixture from which the liquid product phase can be separated by phase separation. After the alcohol excess has been distilled off from the product phase, it must be washed once more with water and finally freed of residual water in vacuo.
  • the yields of tetraalkyl bisphosphates are 12-74%.
  • the base to be used in step b) consists of one or more substances of the formula (Cat n + ) a (X m- ) b.
  • the term “completely water-soluble” in the context of the present invention refers to those liquids which when mixed with water at 25 ° C. regardless of the ratio of the liquid to the water, a homogeneous solution without phase separation result (see Example 7).
  • Tetrachlorbisphosphate used in the process according to the invention can be prepared by known methods, as for example in Indust. Closely. Chem. 1950, Vol. 42, p. 488 or in US 4,056,480 are described.
  • A is preferably a straight-chain C 4 - to C 6 -alkylene radical or A is preferably a group of the general formula (III) in which R 10 and R 11 are identical and are methyl, a grouping of the formulas (V), (VI) or (VII) or preferably A is a grouping -CHR 5 -CHR 6 - (O-CHR 7 -CHR 8 ) a - wherein a is a number from 1 to 2 and R 5 , R 6 , R 7 and R 8 are the same and H is or a grouping - (CHR 5 -CHR 6 ) c -OR 9 -O- (CHR 7 -CHR 8 ) d -, wherein c and d are independently a number from 1 to 2, R 9 is a group of the general formula (II) and R 10 and R 11 are the same and is methyl.
  • A is a radical selected from the group consisting of -CH 2 CH 2 -O-CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 - and -CH 2 -CH (CH 2 CH 2 ) 2 CH -CH 2 -.
  • the alcohols used in the process according to the invention are preferably selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-1-propanol, 1-butanol and 2-butanol. Particular preference is given to using methanol and ethanol.
  • the bases of the formula (Cat n + ) a (X m ) b used in the process according to the invention are preferably ammonium, alkali metal or alkaline earth metal salts. These salts preferably contain as the anion hydroxide, alkoxide, oxide, carbonate, bicarbonate, phosphate, hydrogen phosphate, dihydrogen phosphate or acetate.
  • ammonium hydroxide lithium hydroxide, sodium hydroxide, sodium methoxide, sodium ethoxide, sodium carbonate, sodium hydrogencarbonate, trisodium phosphate, disodium hydrogenphosphate, sodium acetate, potassium hydroxide, potassium tert-butylate, potassium carbonate, potassium hydrogencarbonate, cesium hydroxide, magnesium hydroxide, magnesium oxide, calcium hydroxide, calcium methoxide or calcium oxide.
  • sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate or potassium bicarbonate is particularly preferred.
  • step a) of the process according to the invention at least 4 molar equivalents of alcohol are used per 1 molar equivalent of tetrachlorobisphosphate.
  • the reactants can be reacted in bulk or dissolved in a solvent with each other. Suitable solvents are toluene, heptane and dichloromethane and the excess alcohol used in the reaction.
  • the Tetrachlorbisphosphat is placed in a reaction vessel and the alcohol is added.
  • the alcohol is placed in a reaction vessel and the tetrachlorobisphosphate is metered in. It is also possible to dose alcohol and tetrachloride phosphate in parallel in a reaction vessel. Instead of the pure reactants and solutions of the reactants can be dosed.
  • the P-Cl groups of the tetrachlorobisphosphate are converted by reaction with the alcohol into P-OR groups and hydrogen chloride is liberated.
  • the reaction is preferably carried out at temperatures between -10 ° C and +70 ° C and at pressures between 10 and 6000 mbar.
  • the reactants are brought into contact with one another by suitable measures, in particular by stirring.
  • the hydrogen chloride formed by-product in the reaction is essentially left in the reaction mixture and neutralized in step b) of the process with the base.
  • the hydrogen chloride formed as a by-product is at least partially removed from the reaction vessel in step a). For example, a vacuum is applied or an inert gas such as nitrogen or carbon dioxide is passed through the reaction vessel.
  • step a) may include further optional separation operations, preferably a distillation to remove unreacted alcohol.
  • step b) is not carried out until at least 50% of the P-Cl groups contained in the tetrachlorobisphosphate have been reacted in step a).
  • the conversion of the P-Cl groups can be monitored analytically, preferably by means of 31 P-NMR spectroscopy.
  • the reaction mixture obtained in step a) is preferably brought into contact with the base with thorough mixing.
  • the amount of the base is preferably selected such that the reaction mixture after step b) has a pH of between 6 and 11.
  • the reaction mixture particularly preferably has a pH of between 7 and 10 after step b).
  • the base is preferably introduced into the reaction vessel of step a) in a meterable form.
  • the base is initially charged in a suitable manner in a second reaction vessel and the reaction mixture from step a) is converted into this.
  • suitable metered forms of the base are powders, granules, solutions or dispersions.
  • the base is used in the form of an aqueous solution or dispersion.
  • Very particular preference is given to using a 10 to 60% strength by weight aqueous solution of sodium hydroxide, sodium carbonate, potassium hydroxide and / or potassium carbonate.
  • the base is used in the form of a powder having an average particle size of 0.1 ⁇ m to 2000 ⁇ m.
  • powdered sodium carbonate, sodium hydrogencarbonate, potassium carbonate and / or potassium hydrogencarbonate is especially preferred.
  • the step b) is preferably carried out at temperatures between 5 ° C and 70 ° C and at pressures between 10 and 6000 mbar.
  • Step b) may involve further optional separation operations, preferably a distillation to remove unreacted alcohol from step a).
  • step c) of the process according to the invention water is added to the reaction mixture obtained in step b) and the resulting mixture is thoroughly mixed. As a result, the salt KatCl n is transferred into an aqueous solution.
  • the addition of water can also be carried out in such a way that the water is already introduced in step b) in the form of an aqueous solution or dispersion.
  • Step c) is preferably carried out under the same temperature and pressure conditions as step a).
  • the reaction mixture obtained in step b) is diluted with just enough water to form at least two separate liquid phases spontaneously and without the addition of another solvent in the reaction mixture and all the solids have essentially dissolved.
  • the reaction mixture in the case of water-soluble tetraalkyl bisphosphates in a first clear liquid phase containing predominantly the tetraalkyl bisphosphate, and in a second clear liquid phase, which is predominantly an aqueous solution separates if they are a suitable amount Contains water.
  • the amount of water suitable for achieving the phase separation can easily be determined by simple experiments (see Examples 2 and 3). Preference is given to using between 25 and 50 mol of water, based on one mol of tetrachlorobisphosphate. Particular preference is given to using between 30 and 40 mol of water, based on one mol of tetrachlorobisphosphate.
  • the step c) is preferably carried out at temperatures between 5 ° C and 70 ° C and at pressures between 10 and 6000 mbar.
  • the step c) may preferably include further, optional separation operations, particularly preferably a filtration for the separation of water-insoluble solids or a distillation for the separation of unreacted alcohol from step a).
  • step d) of the process according to the invention the two phases obtained in step c) are separated and the tetraalkyl bisphosphate-containing phase is worked up by methods known per se.
  • the separated product phase may be subjected to further phase separation or several phase separations and, if necessary, to a post-purification, preferably by filtration, clarification, extraction, distillation or drying, or by a suitable combination of these methods.
  • the process according to the invention is preferably used for the preparation of completely water-soluble tetraalkyl bisphosphates. However, it offers advantages even with only partially or not water-soluble tetraalkyl bisphosphates.
  • Each of the four steps of the process may be carried out batchwise or continuously.
  • the entire process may consist of any combination of discontinuous or continuous steps.
  • the inventive method allows the synthesis of wholly or partially water-soluble tetraalkyl bisphosphates in better yield than by the methods known from the prior art and in high purity. It differs significantly from the known processes in that no solvent except water is used in the work-up. It is surprising that the water-soluble tetraalkyl bisphosphates can be separated from the aqueous phase containing the salt-like secondary particles by a liquid-liquid separation and that the separation of the salt-like secondary particles is so completely successful that the end product has only a very low salt content.
  • the mixture had a pH of 8.7 and was stirred for 16 h at 23 ° C and then freed from unreacted ethanol by means of a Vigreux column at 60 ° C and 130 mbar.
  • the remaining suspension was diluted with 500 ml of water and heated to 60 ° C. with stirring. The solid completely dissolved but no phase separation was observed. A work-up on liquid-liquid separation was not possible.
  • Example 7 shows that the considered tetraalkyl bisphosphates are completely or partially miscible with water. Therefore, these substances are according to the manufacturing methods of the prior art only in poor yield or not produced.
  • Examples 2 and 4 to 6 show that tetraalkyl bisphosphates can be prepared simply and in high yield by the process according to the invention. In the process, products of high purity are obtained, as can be deduced from the low acid numbers and sodium contents. It is surprising that the preparation is successfully possible, especially with completely water-soluble tetraalkyl bisphosphates.
  • Fully demineralized water in the sense of the present invention is characterized by having a conductivity of 0.1 to 10 ⁇ S, wherein the content of dissolved or undissolved metal ions not greater than 1 ppm, preferably not greater than 0.5 ppm for Fe , Co, Ni, Mo, Cr, Cu as individual components and not greater than 10 ppm, preferably not greater than 1 ppm for the sum of said metals.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP11151170A 2011-01-17 2011-01-17 Verfahren zur Herstellung von Alkylphosphaten Withdrawn EP2479180A1 (de)

Priority Applications (10)

Application Number Priority Date Filing Date Title
EP11151170A EP2479180A1 (de) 2011-01-17 2011-01-17 Verfahren zur Herstellung von Alkylphosphaten
EP12150718.0A EP2476686B1 (de) 2011-01-17 2012-01-11 Verfahren zur Herstellung von Alkylphosphaten
PL12150718T PL2476686T3 (pl) 2011-01-17 2012-01-11 Sposób wytwarzania alkilofosforanów
CA2764166A CA2764166A1 (en) 2011-01-17 2012-01-13 Process for preparing alkyl phosphates
US13/349,858 US20120184764A1 (en) 2011-01-17 2012-01-13 Process for preparing alkyl phosphates
MX2012000759A MX345082B (es) 2011-01-17 2012-01-16 Procedimiento para preparar fosfatos de alquilo.
CN201210012349.8A CN102603792B (zh) 2011-01-17 2012-01-16 用于制备烷基磷酸酯的方法
JP2012005987A JP6033548B2 (ja) 2011-01-17 2012-01-16 アルキルホスフェートを調製するための方法
KR1020120005161A KR101882518B1 (ko) 2011-01-17 2012-01-17 알킬 포스페이트의 제조 방법
BR102012001156-5A BR102012001156B1 (pt) 2011-01-17 2012-01-17 Processo para a produção de tetraalquilbisfosfatos totalmente solúveis

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP11151170A EP2479180A1 (de) 2011-01-17 2011-01-17 Verfahren zur Herstellung von Alkylphosphaten

Publications (1)

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EP2479180A1 true EP2479180A1 (de) 2012-07-25

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EP11151170A Withdrawn EP2479180A1 (de) 2011-01-17 2011-01-17 Verfahren zur Herstellung von Alkylphosphaten
EP12150718.0A Active EP2476686B1 (de) 2011-01-17 2012-01-11 Verfahren zur Herstellung von Alkylphosphaten

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US (1) US20120184764A1 (ko)
EP (2) EP2479180A1 (ko)
JP (1) JP6033548B2 (ko)
KR (1) KR101882518B1 (ko)
CN (1) CN102603792B (ko)
BR (1) BR102012001156B1 (ko)
CA (1) CA2764166A1 (ko)
MX (1) MX345082B (ko)
PL (1) PL2476686T3 (ko)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115672230B (zh) * 2022-09-29 2023-08-18 云南云天化股份有限公司 一种烷基磷酸酯低聚物制备系统及其制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2782128A (en) 1952-04-16 1957-02-19 Celanese Corp Plasticized cellulose acetate
DE2625878A1 (de) * 1975-06-10 1976-12-23 Monsanto Co Verbesserte hydraulische fluessigkeiten

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1424513A (en) * 1972-06-13 1976-02-11 Ciba Geigy Ag Organic phosphates
JPS5186422A (ja) * 1975-01-22 1976-07-29 Mitsui Toatsu Chemicals Haroarukirurinsanesuterunoseizohoho
JPS5661446A (en) * 1979-10-24 1981-05-26 Ajinomoto Co Inc Stabilizer for halogen-containing resin
CN1163498C (zh) * 2000-08-01 2004-08-25 中国石化上海石油化工股份有限公司 高纯度双烷基磷酸酯的制备方法
DE102005012595A1 (de) * 2005-03-18 2006-09-21 Lanxess Deutschland Gmbh Herstellung von Tri(chlorpropyl)phosphat
DE102005034269A1 (de) * 2005-07-22 2007-01-25 Lanxess Deutschland Gmbh Halogenfreie, flammwidrige Polyurethanschaumstoffe
CN1876661A (zh) * 2006-07-03 2006-12-13 上海大学 脂肪二醇双磷酸双脂肪醇酯的合成方法
CN101302232A (zh) * 2008-05-19 2008-11-12 江苏利田科技有限公司 一种全氟烷基磷酸酯丙烯酸酯及其制备方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2782128A (en) 1952-04-16 1957-02-19 Celanese Corp Plasticized cellulose acetate
DE2625878A1 (de) * 1975-06-10 1976-12-23 Monsanto Co Verbesserte hydraulische fluessigkeiten
US4056480A (en) 1975-06-10 1977-11-01 Monsanto Company Hydraulic fluids

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Diphosphate Ester Plasticizers", INDUST. ENG. CHEM, vol. 42, 1950, pages 488
INDUST. ENG. CHEM, vol. 42, 1950, pages S. 488

Also Published As

Publication number Publication date
MX345082B (es) 2017-01-16
CA2764166A1 (en) 2012-07-17
EP2476686A1 (de) 2012-07-18
US20120184764A1 (en) 2012-07-19
CN102603792A (zh) 2012-07-25
JP2012149064A (ja) 2012-08-09
MX2012000759A (es) 2012-11-27
KR20120083239A (ko) 2012-07-25
BR102012001156A2 (pt) 2013-07-02
PL2476686T3 (pl) 2017-12-29
JP6033548B2 (ja) 2016-11-30
EP2476686B1 (de) 2017-08-02
KR101882518B1 (ko) 2018-07-26
BR102012001156A8 (pt) 2018-12-26
CN102603792B (zh) 2016-08-03
BR102012001156B1 (pt) 2019-09-17

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